Stereochemistry of the hydroperoxides formed during autoxidation of CLA methyl ester in the presence of α-tocopherol

The initial steps in the autoxidation of CLA methyl ester are poorly understood. The aim of this study was to determine the stereochemistry of the hydroperoxides formed during autoxidation of CLA methyl ester in the presence of a good hydrogen atom donor. For this purpose, 9-cis, 11-trans CLA methyl ester was autoxidized in the presence of α-tocopherol under atmospheric oxygen at 40°C in the dark. The CLA methyl ester hydroperoxides were isolated, reduced to the corresponding hydroxy derivatives, and separated by HPLC. The stereochemistry of seven hydroxy-CLA methyl esters was investigated. The position of the hydroxy group was determined by GC-MS. The geometry as well as the position of the double bonds in the alkyl chain was determined by NMR. In addition, the ¹³C NMR spectra of six hydroxy-CLA methyl esters were assigned using COSY, gradient heteronuclear multiple bond correlation, gradient heteronuclear single quantum correlation, and total correlation spectroscopy experiments. The autoxidation of 9-cis, 11-trans CLA methyl ester in the presence of a good hydrogen atom donor is stereoselective in favor of one geometric isomer, namely the 13-(R,S)-hydroperoxy-9-cis, 11-trans-octadecadienoic acid methyl ester. Three types of conjugated diene hydroperoxides are formed as primary hydroperoxides: trans,trans hydroperoxides (12-OOH-8t,10t and 9-OOH-10t,12t), a cis,trans hydroperoxide with the trans double bond adjacent to the hydroperoxide-bearing carbon atom (13-OOH-9c,11t), and a new type of cis,trans lipid hydroperoxide with the cis double bond adjacent to the hydroperoxide-bearing carbon atom (8-OOH-9c,11t). In addition, three nonkinetic hydroperoxides (13-OOH-9t,11t, 8-OOH-9t,11t, and 9-OOH-10t,12c) are formed. This study supports the theory that CLA methyl ester autoxidizes at least partly through an autocatalytic free radical reaction. The complexity of the hydroperoxide mixture is due to formation of two different pentadienyl radicals. Moreover, the stereoslectivity in favor of one geometric isomer can be explained by the selectivity of the two previous steps: the preferential formation of a W-conformer of the pentadienyl radical over the Z-conformer, and regioselectivity of the oxygen addition to the pentadienyl radical.     

Challenges and industry practices for managing software variability in small and medium sized enterprises

Software variability is an ability to change (configure, customize, extend) software artefacts (e.g. code, product, domain requirements, models, design, documentation, test cases) for a specific context. Optimized variability management can lead a software company to 1) shorter development lead time, 2) improved customer and improved user satisfaction, 3) reduced complexity of product management (more variability, same $) and 4) reduced costs (same variability, less $). However, it is not easy for software companies, especially small and medium size of enterprises to deal with variability. In this paper we present variability challenges and used practices collected from five SMEs. Our study indicates that increased product complexity can lead growing SMEs to the time-consuming decision-making. Many of the analyzed medium size of companies also expect improved tool support to help them to boost their productivity when managing increasingly complex products and increasing amount of variants In fact, in many of the analysed SMEs, a high level of automation in design, release management and testing are or become a key factor for market success By introducing the challenges and used practices related to variability the paper deepens understanding of this highly relevant but relatively under-researched phenomenon and contributes to the literature on software product line engineering.     

Pulmonary exposure to single-walled carbon nanotubes does not affect the early immune response against Toxoplasma gondii

ABSTRACT: BACKGROUND: Single-walled carbon nanotubes (SWCNT) trigger pronounced inflammation and fibrosis in the lungs of mice following administration via pharyngeal aspiration or inhalation. Human exposure to SWCNT in an occupational setting may occur in conjunction with infections and this could yield enhanced or suppressed responses to the offending agent. Here, we studied whether the sequential exposure to SWCNT via pharyngeal aspiration and infection of mice with the ubiquitous intracellular parasite Toxoplasma gondii would impact on the immune response of the host against the parasite. METHODS: C57BL/6 mice were pre-exposed by pharyngeal administration of SWCNT (80 + 80 mug/mouse) for two consecutive days followed by intravenous injection with either 1x103 or 1x104 green fluorescence protein and luciferase-expressing T. gondii tachyzoites. The dissemination of T. gondii was monitored by in vivo bioluminescence imaging in real time for 7 days and by plaque formation. The inflammatory response was analysed in bronchoalveolar lavage (BAL) fluid, and by assessment of morphological changes and immune responses in lung and spleen. RESULTS: There were no differences in parasite distribution between mice only inoculated with T. gondii or those mice pre-exposed for 2 days to SWCNT before parasite inoculum. Lung and spleen histology and inflammation markers in BAL fluid reflected the effects of SWCNT exposure and T. gondii injection, respectively. We also noted that CD11c positive dendritic cells but not F4/80 positive macrophages retained SWCNT in the lungs 9 days after pharyngeal aspiration. However, co-localization of T. gondii with CD11c or F4/80 positive cells could not be observed in lungs or spleen. Pre-exposure to SWCNT did not affect the splenocyte response to T. gondii. CONCLUSIONS: Taken together, our data indicate that pre-exposure to SWCNT does not enhance or suppress the early immune response to T. gondii in mice.     

Integrated analytical study for the authentication of five Russian icons (XVI–XVII centuries)

This article presents an integrated approach for the authentication of five Russian icons through the study of their paint materials (elemental composition and stratigraphic mapping), state of conservation and artistic technique. The results of the applied analytical protocol, involving optical and scanning electron microscopy coupled with energy‐dispersive X‐ray spectrometry and Fourier transformed infrared spectroscopy/microspectroscopy, led to the conclusion that the five icons belong to the same group and iconographic school (from Northern Russia) and date from the end of the 16th century to the beginning of 17th century. Because of massive overpainting, the icons “suffered” a change in iconographic style and significance, and restoration treatment brought to light the original painting and its attribution. Identification of the composition of the original chromatic palette used by the iconographer, the stratigraphic mapping and the conservation state of the painting materials, along with the features of the original artistic technique, furnished key elements for the icons' authentication. Here, we present the first experimental data concerning the identification of the authentication characteristics, being part of a large project that has as its final aim the evaluation of the effectiveness and effects of the cleaning agent on the paint layers. Microsc. Res. Tech. 2009. © 2009 Wiley‐Liss, Inc.     

Headspace volatile compounds during osmotic dehydration of strawberries (cv Camarosa): Influence of osmotic solution composition and processing time

The influence of the type of sugar in the osmotic solution and of the time of processing on the volatile compounds of strawberries was studied, in order to optimize the technique as a pre-treatment to further processing. Strawberries of cultivar ‘Camarosa’, cut into 1 cm thick slices, were subjected to osmotic dehydration at 30 °C for 1, 2, 4 and 6 h using either 60% (w/w) sucrose or 60% (w/w) sorbitol solutions. Volatile compounds of fresh and processed strawberry slices were analyzed by static headspace—gas chromatography. Osmotic treatments provoked a loss in volatile compounds due to the migration, mainly of esters, into the osmotic media. The variations in the volatile pattern depended on both time of treatment and type of osmotic solution. The greater changes occurred after 2 h in sucrose; with a promotion of fermentative volatiles (acetaldehyde, ethyl acetate), and a decrease in the other volatiles. Using sorbitol as osmotic agent, the major variations in the volatile pattern occurred after 4 h of osmosis, and the fermentative process was less important than in sucrose, as sorbitol could be less effective in forming a peripheral layer at the fruit surface and/in reducing tissue porosity.     

Coordinated construction logistics: an innovation perspective

Coordinated construction logistics is an increasingly discussed topic in the Swedish construction industry. It is suggested as a means to increase efficiency in transportation, decrease material usage, coordinate health and safety on-site, etc. Much research on construction logistics has been done from a supply chain management perspective, often highlighting construction logistics as a necessary rational tool to improve efficiency in construction industry. However, could there be other ways to study this phenomenon? The purpose of this paper is to map empirically found coordinated construction logistics models and explore them as different types of innovation. The findings suggest that coordinated construction logistics models should be regarded as not being a fully embedded innovation as they have not yet changed the processes in the way they set out to do initially. Furthermore, differences are identified between company-based models, project-based models and system-based models, and suggest that differences in, for example, development, impact and objectives should be regarded both when conducting research on and when implementing coordinated construction logistics in practice. Finally, it is concluded that commitment, communication and cooperation are important when implementing coordinated construction logistics, which is in line with findings within the supply chain management literature.     

Carbon nanotube micropillars trigger guided growth of complex human neural stem cells networks

Nano Research - New strategies for spatially controlled growth of human neurons may provide viable solutions to treat and recover peripheral or spinal cord injuries. While topography cues are known...     

Who controls our data? The legal reasoning of the European Court of Justice in Wirtschaftsakademie Schleswig-Holstein and Tietosuojavaltuutettu v Jehovan todistajat

This paper analyses two judgments from the European Court of Justice. Both were delivered soon after the new Data Protection Regulation became applicable. The argumentation in the judgments provides timely clarification on certain key concepts in European data protection law. As the analysis will show, the ECJ continues its broad interpretation of the parties responsible for data processing. The judgments are generally compatible with the Court’s previous case law, which seeks to fill any potential gaps in the protection of individuals’ privacy rights. Hence, the aims of data protection rules are predominately interpreted by the Court within a fundamental rights framework. Even though the cases have certain significant differences, the conclusions to be drawn are similar: the argumentation of the Court is focused on data protection throughout. Moreover, the Court emphasises strong protection of personal data in all kinds of situations, even those where other rights could also be relevant.     

Removal of Ethylenediaminetetraacetic acid (EDTA) from Pulp Mill Effluents by Ozonation

Ozone application was investigated for its effectiveness in the removal of ethylenediaminetetraacetic acid (EDTA) from bleaching effluent. The objectives were to compare the efficiency of ozone reaction on Na-EDTA solution with pure Fe³⁺-EDTA complex and EDTA complexes in bleaching effluent, and to test if changing pH and addition of hydrogen peroxide (H₂O₂) increases the removal of EDTA. Small ozone doses destroyed high proportions of Na-EDTA. This effect was diminished when EDTA formed complexes with other metal ions. It was shown that EDTA present in bleaching effluent was more easily oxidizable than in pure Fe³⁺-EDTA solution. Variation of initial pH value had no significant influence on the removal of Na-EDTA. Addition of hydrogen peroxide did not increase degradation of EDTA in bleaching effluent.